5-hydroxy-hydrindene-ortho-carboxylic acid



V 45 S-hydroxy-dydrindenepatented Apr. 27, 1937 UNITED "STATES PATENTOFFICE Werner Zerweck, Ernst Korten, amlMax Schu brt,Frankfort-on-the-Main-Fechenheim, Ger.- many, assignors to GeneralAniline Works, Inc.-, New York, N. Y.; a corporation of Delaware NDrawing. A Application October 4, 1935, Serial 7 No. 43,510. In GermanyOctober 4, 1934 1 Claim.

Our invention relates to a new compound of the hydrindene series andprocess of making same and particularly to a compound of the formula:

0 noorc v CH1 C"- 0H/ wherein the carboxylic acid radicle stands inortho-position to the hydroxy group.

The new productis obtained on heating an alkali salt of5-hydroxy-hydrindene with carbon dioxide, whereby a newortho-hydroxycarboxylic acid is formed. This compound may be condensedaccording to known methods with an aliphatic,:aromatic or heterocyclicamine in order to form the corresponding acid amide. V

The newproduct may .be used as an intermediate for the production ofdyestulfs, particularly of azodyestufis. i

In order to further illustrate our invention the following examples aregiven; but we wish it, however, to be understood that our invention isnot limited to the particular pro-duct or 2 reaction conditions statedtherein.

Example 1 40 means of an acid; then it is isolated by filtration andwashed in order to remove certain impurities. By dissolving in a hotsodium acetate solution and cooling a crystalline precipitate isobtained, which is then converted into the free ortho-carboxylic acid.This acid of the probable formula:

yields with ferric chloride a dark navy blue coloration and crystallizesfrom monochlorobenzene 55 in colorless needles of melting point 198 C.

The same carboxylic acid is obtained by dry ing at first in vacuo, whilestirring, the 5-hydroxy-hydrindene with an excess of caustic potash andtreating the condensation product with carbon dioxide; by using insteadof the free caus- 5 tie potash an equivalent amount of caustic soda andworking otherwise as indicated above, the same acid results.

Example 2 10 A current of carbon dioxide of moderate speed is introducedat-a starting temperature of 100 C. while stirring intensely, into anautoclave provided with an oilbath and a strong stirring apparatus,containinglZO parts of the dry potasl5 siumsalt of the5-hydroxy-hydrindene. Simultaneously the temperature is brought up to200 C. during 6 hours. A certain quantity of free 5- hydroxyhydrindenetogether, with passing gases are blown away throughajoining wide cooler.The hydroxyhydrindene solidifies in the cooler. Then the residueremaining in the vessel is dissolved in water and filtered, the filtrateis acidified by means of hydrochloric acid, filtered and washed withwater in order to remove certain impurities. The crude acid is thendissolved in a dilute acetate solution as described in Example 1,filtered and reciprocated by means of hydrochloric acid.

The 5-hydroxy-hydrindene-ortho-carboxylic acid thus obtained with a goodyield is identical to that obtained according to Example 1.

Example 3 A mixture of 17.8 parts of5-hydroxy-hydrindene-ortho-carboxylic acid, obtained according toExample 1, 300 parts of toluene and 9.3 parts of aniline is heated toabout 70 C. and into this mixture 6 parts of phosphorus trichloride areallowed to flow at the same temperature while stirring. Then the mass isheated to boiling until the evolution of hydrochloric acid ceases, themass is poured into a sodium carbonate solution, the toluene is blownout with steam, the residual mass is filtered off and the residue iswashed with water. The anilide thus obtained of the formula:

HO OH X\ @HNom may be purified by dissolving it in a dilute caus ticsoda solution and acidifying by means of hydrochloric acid. It is easilysoluble in chlorobenzene, difficultly soluble in petrol and glacialacetic acid, from which it crystallizes in bundles 5 of colorlessneedles of melting point 187 C.

Example 4 8 parts of 5-hydroxy-hydrindene-o-carboxylic 10 acid areheated to 70 C. with the addition of 150 parts of dimethylaniline and 12parts of p-naphthylamine. At the same temperature 5 parts of phosphoroustrichloride are allowed to drop in, while stirring, whereby a clearsolution 15 is formed. The mass is again heated during some hours to100-105 0., poured into an excess of hydrochloric acid, thenfiltered andwashed with water until acid-free. The p-naphthylamide of5-hydroxy-hydrindene-ortho-carboxylic acid thus obtained of the formula:

may be purified by dissolving it in a dilute caustic alkali solution,filtration and acidification by means of hydrochloric acid. It is rathersoluble in benzene, difiicultlysoluble in glacial acetic acid andcrystallizes therefrom in colorless prisms of melting point 229 C.

In the same manner further arylides may be obtained, generally beingcolorless crystalline powders; the u-naphthylamide thus obtained meltsin a pure state at 210 0., the condensation product of the5-hydroxyhydrindene-ortho- -"carboxylic acid with para-chloranilinemelts in a pure state at 230 0., that withchloroaminohydroquinonedimethylether of the formula:

HaN

at C that with chloroaminoresorcinedimethylether of the formula:

HzN

OCH:

which crystallizes in colorless needles of 198 melting point, and yieldswith ferric chloride 2.

dark navy blue coloration. r

WERNER, :ZERWECK; ERNST KORTEN.

MAX SCHUBERT.

